L. Echegoyen, T. Torres et al.
FULL PAPER
dichlorobenzene (ODCB; 1 mL) were refluxed under argon overnight.
After flash chromatography (SiO2, toluene) the fulleropyrrolidine ±
phthalocyanine derivative 1b was afforded. MS (FAB): m/z: 1521 [M
TMS): d 192.2, 191.8, 153.3, 153.2, 153.1, 138.3, 134.8, 134.4, 133.0, 131.8,
130.8, 127.5, 123.8, 122.2, 120.4, 119.1, 36.2, 36.1, 32.5, 32.3; IR (KBr): nÄ
3423, 2956, 1697, 1610, 1488, 1394, 1257, 1181, 1085, 747 cmÀ1; UV/Vis
(CHCl3): lmax (log e) 344 (4.7), 621 (4.3), 643 (4.5), 680 (4.9), 693 nm (5.0);
H ], 800 [M À C60] , 720 [C60] .
MS (FAB): m/z: 711 [M H ]; C45H42N8O (710.88): calcd: C 76.03, H 5.96,
Tri-tert-butyliodophthalocyanine (3a): Lithium metal (37 mg, 5.33 mmol)
in 1-pentanol (1 mL) under an argon atmosphere was refluxed for 15 min.
The suspension was cooled down to room temperature and 4-iodophtha-
lonitrile (127 mg, 0.5 mmol) and 4-tert-butylphthalonitrile (553 mg,
3 mmol) in amyl alcohol (1 mL) were added and the mixture was refluxed
overnight. The solvent was evaporated and the crude product obtained was
purified by chromatography (Al2O3, hexane/dioxane 5:1) to yield 3a
N 15.76; found: C 76.28, H 6.14, N 15.51.
5b: Yield: (41 mg, 76%) as a blue solid; m.p. > 2508C; 1H NMR (500 MHz,
CDCl3, 258C, TMS): d 10.1 (br s, 1H; CHO), 9.5 ± 8.7, 8.5 ± 7.3 (br, 12H;
arom H), 1.7 ± 1.5 (br, 27H; C(CH3)3); 13C NMR (125 MHz, CDCl3, 258C,
TMS): d 187.3, 153.4, 138.5, 131.8, 128.2, 123.8, 36.0, 32.3; IR (KBr): n
3416, 2955, 2903, 1697, 1611, 1486, 1392, 1331, 1278, 1256, 1180, 1085, 1047,
747 cmÀ1; UV/Vis (CHCl3): lmax (log e) 353 (4.8), 610 (4.3), 639 (4.4), 670
1
(69 mg, 17%) as a blue solid. M.p. > 2508C; H NMR (500 MHz, CDCl3,
258C, TMS): d 9.0 ± 7.3 (m, 12H; arom H), 1.9 ± 1.7 (m, 27H; C(CH3)3),
(À3.7) ± (À4.5) (m, 2H; NH); 13C NMR (125 MHz, CDCl3, 258C, TMS):
d 153.5, 153.4, 128.1, 122.5, 119.2, 36.5, 36.4, 32.6, 32.5, 32.4, 32.3; IR
(KBr): nÄ 3416, 3290, 2954, 2865, 1616, 1503, 1482, 1392, 1318, 1257, 1091,
1008, 749 cmÀ1; UV/Vis (CHCl3): lmax (log e) 343 (4.9), 609 (4.4), 641
(5.0), 698 nm (5.0); MS (FAB): m/z: 773 [M H ]; MALDI-TOF: m/z: 773
[M H ]; C45H40N8OZn (774.24): calcd: C 69.81, H 5.21, N 14.47; found: C
69.65, H 5.38, N 14.23.
Method B: A solution of tri-tert-butyl-vinylphthalocyanine (4a) (47 mg,
0.066 mmol) or tri-tert-butyl-vinylphthalocyaninatozinc(ii) (4b) (40 mg,
0.052 mmol) in CH2Cl2 (30 mL) was cooled at À788C, and then an excess
of ozone was passed through the mixture for 3 min (the solution turned
dark green and then light brown). After the reaction mixture was purged
with argon for 30 min at À788C, it was treated with dimethyl sulfide
(3 mL). The cold bath was removed and the mixture was allowed to stir at
room temperature for 2 h. Removal of the solvents under reduced pressure
provided a residual solid which was purified by chromatography as in
Method A.
(4.6), 666 (5.1), 695 nm (5.0); MS (FAB): m/z: 809 [M H ]; C44H41N8I
(808.76): calcd: C 65.34, H 5.11, N 13.85; found: C 65.07, H 4.99, N 13.64.
Tri-tert-butylvinylphthalocyanine (4a)
Method A: A mixture of tri-tert-butyl-iodophthalocyanine (3a) (69 mg,
0.085 mmol) and [Pd(PPh3)4] (5 mg, 0.0043 mmol) in toluene (50 mL) was
stirred under argon. Then tributyl(vinyl)tin (50 mL, 0.17 mmol) was added.
The reaction mixture was heated at 1008C for 10 h. The solvent was
evaporated and the solid residue was triturated with methanol, filtered, and
chromatographed (Al2O3, hexane/dioxane 5:1) to afford 4a (54 mg, 90%)
as a blue solid. M.p. > 2508C; 1H NMR (500 MHz, CDCl3, 258C, TMS):
d 9.0 ± 7.5 (m, 12H; arom H), 7.1 ± 6.8 (several m, 1H; vinyl H), 6.2 ± 5.9
(several dd, 1H; vinyl H), 5.65 ± 5.4 (several m, 1H; vinyl H), 1.9 ± 1.7 (m,
27H, C(CH3)3), À3.1 ± À 3.6 (m, 2H, NH); 13C NMR (125 MHz, CDCl3,
258C, TMS): d 153.4, 153.3, 137.9, 135.5, 133.3, 127.8, 122.3, 118.9, 115.2,
36.4, 32.5; IR (KBr): nÄ 3417, 3290, 2955, 2903, 2865, 1616, 1503, 1482,
1465, 1392, 1318, 1257, 1091, 1008, 828, 749 cmÀ1; UV/Vis (CHCl3): lmax (log
e) 344 (4.8), 607 (4.3), 647 (4.6), 668 (5.0), 702 nm (5.1); MS (FAB): m/z:
5a: Yield: (3.8 mg, 8%).
5b: Yield: (4 mg, 10%).
4-Vinylphthalonitrile (6)
Method A: To a stirred solution of 4-iodophthalonitrile (101 mg, 0.4 mmol)
and [Pd(PPh3)4] (21 mg, 0.02 mmol) in toluene (25 mL) under argon
atmosphere, tributyl(vinyl)tin (0.24 mL, 0.8 mmol) was added. The mixture
was heated at 1008C for 12 h. After removal of the solvent under reduced
pressure, dichloromethane (20 mL) was added and the solution was washed
with water, dried, and the solvent was evaporated. The residue was purified
by flash chromatography (SiO2, CH2Cl2/hexane 2:1) to give 6 (60 mg, yield:
97%) as a white solid. M.p. 618C; 1H NMR (200 MHz, CDCl3, 258C,
TMS): d 7.82 (d, 4J(H,H) 1.6 Hz, 1H; arom H), 7.80 (d, 3J(H,H)
8.2 Hz, 1H; arom H), 7.74 (dd, ,4J(H,H) 1.6, 3J(H,H) 8.2 Hz, 1H; arom
H), 6.74 (dd, 2J(H,H) 10.8, 3J(H,H) 17.6 Hz, 1H), 5.96 (d, 3J(H,H)
709 [M H ]; C46H44N8 (708.91): calcd: C 77.94, H 6.26, N 15.81; found: C
77.64, H 6.02, N 15.61.
Method B: Lithium metal (11 mg, 1.6 mmol) was dissolved under an argon
atmosphere in amyl alcohol (1 mL) and the mixture was refluxed for
15 min. After cooling, 4-tert-butylphthalonitrile (166 mg, 0.9 mmol) and
4-vinylphthalonitrile (6) (16 mg, 0.1 mmol) were added and the mixture
was refluxed overnight. Column chromatography (two SiO2 columns,
CH2Cl2/hexane 2:1 and CH2Cl2/hexane 1:1) gave 4a (8 mg, 11%).
2
17.6 Hz, 1H), 5.62 (d, J(H,H) 10.8 Hz, 1H); C10H6N2 (154.17): calcd: C
77.91, H 3.92, N 18.17; found: C 77.66, H 4.13, N 18.01.
Tri-tert-butylvinylphthalocyaninatozinc(ii) (4b): To a stirred solution of
tri-tert-butyliodophthalocyaninatozinc(ii) (3b) (44 mg, 0.05 mmol),
[Pd(PPh3)4] (3 mg, 0.0026 mmol) in toluene (50 mL) under an argon
atmosphere, tributyl(vinyl)tin (44 mL, 0.15 mmol) was added and the
solution heated at 1008C for 10 h. The solvent was evaporated and the
residual solid was triturated with methanol, filtered, and chromatographed
(SiO2, hexane/dioxane 4:1) to yield 4b (35 mg, 91%) as a blue solid. M.p. >
2508C; 1H NMR (500 MHz, CDCl3, 258C, TMS): d 8.7 ± 7.3 (br, 12H;
arom H), 7.0 ± 6.7 (br, 1H; vinyl H), 6.0 ± 5.7 (br, 1H; vinyl H), 5.5 ± 5.35 (br,
1H; vinyl H), 1.7 ± 1.5 (br, 27H; C(CH3)3); 13C NMR (125 MHz, CDCl3,
258C, TMS): d 153.5, 139.0, 138.0, 128.0, 125.9, 122.5, 36.1, 32.3; IR
(KBr):nÄ 3416, 2953, 2901, 2863, 1614, 1489, 1392, 1331, 1256, 1089, 923,
747 cmÀ1; UV/Vis (CHCl3): lmax (log e) 354 (4.7), 616 (4.2), 682 (5.0), 718
Method B: Vinylmagnesium bromide (4 mL, 4 mmol, 1M THF), ZnCl2
(8 mL, 4 mmol, 0.5M THF) and dry THF (10 mL) were added at À788C to
a three-neck flask equipped with a reflux condenser, and the mixture was
warmed up to 08C over 30 min. Then, a solution of 4-iodophthalonitrile
(1 g, 3.94 mmol), and a catalytic amount of [Pd(PPh3)4] in freshly distilled
THF was added by cannula and the mixture heated to 458C overnight.
Water (100 mL) was added and the mixture was extracted with Et2O (3 Â
50 mL). The combined organic layers were washed with brine, dried,
filtered through a plug of silica, and reduced under pressure to obtain a
white-yellowish solid, which upon purification by flash chromatography
(SiO2, CH2Cl2/hexane 4:1) afforded 6 (425 mg, 70%).
4-Formylphthalonitrile (7): A solution of 4-vinylphthalonitrile (6) (63 mg,
0.41 mmol) in CH2Cl2 (8 mL) was cooled at À788C, an excess of ozone was
passed through the mixture (the solution becomes deep blue in color when
saturated with ozone). After the reaction mixture was purged with argon
for 30 min at À788C, it was treated with dimethyl sulfide (0.2 mL). The
cold bath was removed and the mixture was allowed to stir at room
temperature for 30 min. Removal of the solvents provided crude for-
mylphthalonitrile, which was purified by flash chromatography (SiO2,
CH2Cl2/hexane 4:1) to furnish 7 (58 mg, 90%); m.p. 1388C. 1H NMR
(200 MHz, CDCl3, 258C, TMS): d 10.1 (s, 1H; CHO), 8.25 (d, 4J(H,H)
1.53 Hz, 1H), 8.18 (dd, 4J(H,H) 1.53, 3J(H,H) 7.96 Hz, 1H), 7.97 (d,
3J(H,H) 7.96 Hz, 1H); 13C NMR (65 MHz, CDCl3, 258C, TMS): d 188.2
(CHO), 138.8, 134.5, 133.7, 133.2, 120.2, 117.2, 114.5 (CN), 114.3 (CN); IR
(sh) nm (4.6); MS (FAB): m/z: 771 [M H ]; C46H42N8Zn (772.27): calcd:
C 71.54, H 5.48, N 14.51; found: C 71.24, H 5.59, N 14.23.
Tri-tert-butylformylphthalocyanine (5a) and tri-tert-butylformylphthalo-
cyaninatozinc(II) (5b)
Method A: To a suspension of OsO4 (200 mg; 1% wt. of poly(4-vinyl-
pyridine)) and tri-tert-butylvinylphthalocyanine (4a) (54 mg 0.076 mmol)
or tri-tert-butyl-vinylphthalocyaninatozinc(ii) (4b) (54 mg, 0.07 mmol) in
THF (100 mL) was added dropwise a saturated aqueous solution of NaIO4
(30 mL) at room temperature. The reaction mixture was stirred at this
temperature for 16 h, then filtered over celite, and after the solvents were
evaporated under reduced pressure, the crude products were purified by
flash chromatography (SiO2, hexane/ethyl acetate 9:1 changing to 6:1).
5a: Yield: (40 mg, 74%) as a blue solid; m.p. > 2508C; 1H NMR (500 MHz,
CDCl3, 258C, TMS): d 10.09 (br s, 1H; CHO), 9.6 ± 9.1, 8.5 ± 7.3 (m, 12H;
arom H), 1.75 ± 1.5 (m, 27H; C(CH3)3); 13C NMR (125 MHz, CDCl3, 258C,
ꢀ
(KBr): nÄ 3106, 3071, 3047, 2878 (CHO), 2233 (C N), 1709 (C O), 1567,
1381, 1149, 1096, 850, 752 cmÀ1; MS (EI) m/z (%): 156 (61) [M ], 155 (100)
[(M À H) ], 127 (40) [(M À CHO) ]; C9H4N2O (156.14): calcd: C 69.23, H
2.58, N 17.94; found: C 69.03, H 2.26, N 17.68.
3606
ꢁ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
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Chem. Eur. J. 2000, 6, No. 19